Diazotype layers having cyan acetyl amides as azo components



Patented Jan. 2, 1 951 UNITED STATES DIAZOTYPE LAYERS HAVINGCYAN'AGETYIJ AMIDES AS AZO COMPONENTS William H..von Glahn, Loudonville,and Lester N. Stanley, Delmar,.-N. Y., assignors to Generazb Aniline &Film Corporation,.New. York Nr-Y a corporation of Delaware.

No. Drawing. Application Au SerialNo. 766,875

6" Claims.

This invention relates toa diazotype process and more. particularly tothe use of organic esters and. nitriles. containing active methylenegroup as the azo components in the light. sensitive layer of. adiazotypereproduction' medium min a: developing solution for the exposeddiazotype image.

Inv the reproduction of mechanical drawings, printed material, picturesor other originals to be copied, it is of particular advantage in manycases to make first an intermediate print or transition print on atransparentdiazotypev copying material by exposingthe. transparentsensitized. diazotype material. to actinicrays, such as. ultra. violetlight; by either. the. printing through. 01'. reflex process andithendeveloping the'diazotype material. The development of. such diazotypeprints may be carried out-by any of the develop.-

ing methods known to the artrfor development" ofv exposed diazoty-pematerials. Thus,. where a. two-component: system is employed containing.the azo component in. the. light sensitivelayer.

with the diazo compound; development is effected by passing. the exposeddiazotype. through am.- monia vapors, and where. a. one-componentsystemis employed which containsthe diazo come poundv as the only dyecomponent in the light sensitive layer, the image is. developed. bytreator'valuable originalwhicl'iz wouldfbeadversely af;- fected, if notdestroyed, in the repeatediexposures necessary to make thedeslred'number of" copies.

It is essential inthe so-called reflex process; where; i

Q such'as phloroglucinol andaresorcinol... Thesesazo. components areacetoacetyl" derivatives ofmonothe diazotype copy material"v issuperimposed on the opaque original to be copied and" the. light. forexposure of the diazotype' material passes through; it and is reflected.by the surface oithe. original.-'- The efii'ciency. ofithe;processinvolving the production of a transition or intermediate.

print depends. upon the opacityof the azo. dye? ing half-tones or toolightlines theydo not proimage produced "upon. such'intermediateortransi.- tion' print to ultraviolet li'ghtta'nd upon .the transparencyoffthe. background t'oz. such light. It. die.- pen'ds also; upon thevisual density of. the. image. produced on the: intermediate-yertransitionv print; since'image's oi.poorivi'sual. ;iinz;.suoh.asli'ghtl. yeilow's; on: a white or: transparent: background',..

though; they may have" the; desired degree: or

opacity-to-ultravioleh light, nevertheless have-thedisadvantages ofrenderingdifiicult the detection of flaws: in the intermediate image.-Withsuch prints it isr'necessary to-make a contrastprint. i

goodavisualidensity from the intermediate: before suchiflaws canebedetectedthereby introducing: an. additional and unnecessary step;

Prints? of: adeep-cclorhaving good, visual :den.--

l0 sity; can-.b'e obtained vfrom. diazotypes using" azodensity of thecolorreproducing the image, its

actinic opacity or photographic density isnotsufe ficient to reproducethe image satisfactorily in subsequent copies. The-azo: dye. componentused for the production of transition print images must be such as toproducerupomcouplingawith the:

diazo compound employed a color which will sufficiently absorb theultraviolet lightinc'ident upon it during exposureto'preventlight-decomposition of the diazo compound in the-areas to-be repro hduced fromthetransition copies. Colors of good visual density donotneeessarilyhave this property. It is well'known, for instance, thatblues, such as" are produced from azo components like phloroglucin,are-very poor in their ultraviolet absorption characteristics.

Azo component's, sueh-asresorcinol, have heretofore been employed in theproduction of diazotype prints in order to obtain color images havingthe necessary light absorption characteristics for transition printing.Resorcinoliwill" reproduce the:imageron,the:transition print in a sepiaor orange-brown color which has good opacity to ultraviolet light andhas" sufiicient depth of color orvisualZ-d'ensity to assure detec- 40tion oi printing flaws and the like in the devel- Other azo components,

oped intermediate print. have. been suggested which will produce imagesof, good opacity-on covering" power when used in combination witirpolyhydroxy azo components,

as shaders for other" colorswhich may lack the necessary-i coveringpowerr,. particularly inv copy? duce satisfactory images when used asself colors, that is, when the acetoacetyl derivatives of 5 mono-amines,such. assthe cyclohexyl acetoacetic 'acid iamide and. the like disclosedin Patent 7 1,98 9,065,,ares.used as. the" onl'yazo' components forthie'develbpment' of a diazotype printy'the image produced does not havea satisfactory shade or tone value. a

It has now been found that certain cyanacetylamides containing an activemethylene groupare especially effective as azo components for di azotypereproduction. These cyanacetylamides containing active methylene groupsmay be represented by the formula lene or Z S-dihydroXynaphthalenesulfonic acid,

excellent neutral blacks having improved opacity to ultraviolet lightare obtained. Examples of cyanacetylamides having active methylenegroups of this class are Cyanacetamide f i 2. Cyanacetanilideerr-omoo-nnQ 3. p-I-Iydroxy cyanacetanilide 4. Cyanacetbenzylamide 5.l-1nethyl-2w-cyanacetyliminodihydroquinoline.

en meled-um 6. Cyanacetylurea CN-CHzCO-NHCONH:

7. Cyanacetylthiourea oN-omc ONH (ll-NH:

Cyanacetylguanidine I v oN-o Hio o-NH-c-Nm 9. CyanacetylcyanamideCNCH2CONHCN 10. Cyanacetylethylurethane cn-onzco-mncoocgml 11. 1 wcyanacetylimino 2 methyl-E-ethoxydihydrobenzothiazole Y In thepreparation of diazotype materials in tended for useas intermediate ortransition print media in accordance with this invention, a suitabletransparent base, such as transparentized paper, cellulose acetate filmor other transparent material, iscoatedby means known to the art with alight sensitive composition containing suitable diazo compounds. Whereit is desired to make a twmcomponent diazotype layer on the support orbase material for development by the dry developing method. the azocomponent is also incorporated into the coating composition. Whereone-component diazotype layers are desired, the azo component is addedto an alkaline developing solution and after exposure of the diazotype,the exposed image is developed by contacting with the alkalinedeveloping solution by means known to the art. In the preparation ofcoating compositions for two-component diazotype layers, the coatingsolution may also contain such other materials as are ordinarily used inthe preparation of diazotype twoeoinponent light sensitive coatingcompositions. These include stabilizing materials, such as citric acid,phosphoric acid and thiourea; swelling agents for cellulose acetate andother cellulosic ester bases, such as isopropanol, and shadeintensifying agents, such as nickel sulfate. In preparation of lightsensitive layers on paper for the production of neutral black images ordark tone images which may or may not be intended for reproduction offurther copies, it is preierable to employ a two-component coatingcomposition which will contain one or more dark tone producing azocomponents, preferably such as will produce blue shades with the diazocompounds employed in combination with the nitrile acetyl, amide azocomponents of this invention. The diazo compound or compounds and. otherad juvants are added to the coating composition and the paper used as acarrier for the light sensitive layer is coated in the same manner asthe trans parentized paper or oellulosic film base material in the caseof the transition print media. As diazo compounds, any suitable lightsensitive diazo compound which will couple with the azo components toreproduce a colored image, may be employed. We prefer, however, to usediazo compounds derived from p-diamines of the bon zene series,particularly when two-component coating compositions are employed. As iswell known in the art, this class of diazo compounds is especiallsuitable for the production of twocomponent diazotype photosensitizedpapers. Other diazo compounds have been found suitable for use, such asdiazo anhydrides of aminohyethyl N-ethylaminoA aminobenzene p phe'riyl-4-ami-no-N,:N-dihydroxyethylaniene :diamine: line; p- (4 -ethoxyphenyl)-.a'm'ino -i2,'5-diethoxyaniline; 1-N-ethylamino-2-methyl-4-aminobenzene; 1-dimethyl-amino-3-methoxy-4-aminobenacne;N;N-dimethyam'ino-p-aminobenzenej 1-'d 'i-" methylamin-o 3methyl-4-aminobenzene-; -'p-' .aminophenyl morpholine and2-amino-1-naph- 'thol-S-Sulfon-ic acid. The diazo derivatives 'ofExample 1 Transparentized paper is coated with a coating solutioncontaining the following ingredients per 10000. of water containing 5%of alcohol:

4.0grams cyanacetanilide 3.3 grams N-methyl-N-hydroxyethyl-p-benzenediazonium chloride-ZnClz double salt 4.0 grams thiourea 8.0 grams citricacid 2.0 grams phosphoric acid. 5.20 grams ZnCla [The resulting coatedpaper or diazotype good precoupling stability during prolonged stor-'age. After drying the coating in the usual manner, the diazotyp'e isexposed to light under a positive and the image developed with ammoniafumes. The image of the positive original is thus obtained .in a lightbrown colored positive print. The dye or color areas reproducing theimage have good fade and 'wa'sh-fastness properties and excellentopacity to ultra-violet light. The print can be used as a transitionprint for the reproduction of further diazotype copies or other photoreproductions.

Example .2

-"-*irans parentized paper is coated with a coating solution containingthe following ingredients per 100 cc. of water containing 5% of alcohol:

2.8 grams cyanacetylurea 3.8 grams .N-methyl-N-hydroxyethyl-PebenzeneExample 3 I Transparentized paper is coated with a diazotype coatingsolution containing the following ingredients per -:cc.-nf watercontaining 5% of alcohol:

34) grams cyanacetamide 32 grams l-iitil -ethy1amino)-'2-'methyl-&-1benzene diazonium chloride-ZnCh double salt 4.0 gramsthiourea 8.0 grams citric acid 2.0 grams phosphoric acid 5.0 grams ZnClaThe resulting coated paper-tor .diazot-ype mate-' rial has goodprecoupling stability during pro- After drying the coating in the'longed storage. usual manner, the diazotype is exposed .to light under apattern, design or picture to be reproduced and the image .is developedwith ammoniafumes... A positive image of the original is thus obtainedin a Sepia color. The dye :or color areas reproducing the densitysections of;

the original have good fade and wash-fastne's's properties and showexcellentopacity to ultraviolet .light. The print, therefore, can be:used as :a transition or intermediate print for the reproduction offurther diazotype copies or other photo -reproductions.

Upon substituting 3.5 grams cyanacetbenzyl-- amide,, 3.6 grams .1-iNethyl-N hydroxyethyleamino) -3-methyl-4-benzene diazonium chlorideZnGlz-double salt or 3.3 grams cyanacetylethylurethane and 3.5 gramsN-ethyl-N-hydroxye'thylp-benzene diaaonium chloride-ZnClz' double .salt

for the coupling component and .diazo compound of this example,respectively, diazotype materials having the same properties andreproducing the original in images of the same color as above areobtained.

Example A diazotype---co.ating solutioncontainingthefollowingaingredients per 1-00 cc. of a 5% aqueous solutionof alcohol is made up:

.Upon .using this coating solution to produce a diazotype coating ontransparentized diazotype paper stock-and upon drying the coating in theusual manner, a-diazotype layer having excellent precouplingstability isobtained. Upon exposing "tne thus sensitized .transpa-rentized paper tolight under a pattern, design or picture to .be reproduced anddeveloping with ammonia fumes, a reproduction of the original in a blackshade on "a' clear' background is obtained. This'dy'e image has goodfade and wash-fastness properties and excellent opacity to ultravioletlight. Therefore, it can be used as a transition or intermediate printin the reproduction of further diazotype copies or other photoprintcopies.

If a non-transparentized diazotype paper stock is used in the coatingstep and the usual diazotype procedure followed of drying and exposingunder a pattern followed by ammonia development, an

ground results.

Example 5 Transparentized diazotype paper stock is coated with a coatingsolution containing the following ingredients per 100 cc. of watercontaining 5% of alcohol:

3.2 grams of cyanacetylthiourea 3.5 grams N,N-dihydroxyethyl-p-benzenediazonium ChIOIidG-CdClz double salt 4.0 grams thiourea 8.0 grams citricacid 2.0 grams phosphoric acid 5.0 grams ZnClz The resulting coatedpaper or diazotype material has good precoupling stability duringprolonged storage. After drying the coating in the usual manner, thediazotype is exposed to light under a pattern or other original to bereproduced and the image is developed with ammonia fumes. The image ofthe original is thus obtained in a sepia colored positive print. The dyeor color areas reproducing the density areas of the original have goodfade and wash-fastness properties and excellent capacity to ultravioletlight. The print, therefore, can be used as a transition or intermediateprint for the reproduction of further diazotype copies or otherphotoreproductions.

Upon substituting for the 3.2 grams cyanacetylthiourea couplingcomponent and the 3.5

grams N,N-dihydroxyethyl-p-benzene diazonium chloride-CdClz double saltdiazo compound of this example, th following combinations of couplingcomponents and diazo compounds, diazotype coatings having the sameproperties as the coatings of this example are obtained:

(1) 3.3 grams cyanacetylguanidine 3.2 grams N-phenylamino-p-benzenediazonium acid sulfate 3.1 grams cyanacetylcyanamide 3.5 grams l-(N-ethyl N hydroxyethylamino) -3-methyl benzene-p a diazoniumchloride-ZnClz double salt 3.4 grams cyanacetylethylurethane 3.8 gramsN,N-cliethylamino benzene-pdiazonium chloride-ZnClz double salt 3.4grams 1-w-cyanacetylimino-2-methyl-5- of the benzene series and an azocomponent selected from the class consisting of cyanacetylamides of thefollowing formula CNCH2COR wherein R is a nitrogen containing radical ofthe class consisting of amino, arylamino, aralkylamino,a-iminodihydroheterocyclic, carbamido, thiocarbamido, carbamidino,cyanimido, and carboalkoxyimido radicals.

2. A diazotype photoprinting material comprisinga light sensitivediazonium salt of a p-diamine of. the benzene series and as an azocomponent cyanacetanilide having the structural formula 3. A diazotypephotoprinting material comprising a light sensitive diazonium salt of ap-diamine of the benzene series and as an azo component cyanacetylureahaving the structural formula 4. A diazotype photoprinting materialcomprising a light sensitive diazonium salt of a p-diamine of th benzeneseries and as an azo component cyanacetbenzylamide having the structuralformula ON-CHzC ONHCHT 5. A diazotype photoprintlng material compris inga light sensitive diazonium salt of a p-diamine of the benzene seriesand as an azo component cyanacetamide having the structural formula 6. Adiazotype photoprinting material comprising a light sensitive diazoniumsalt of a p-diamine of the benzene series and as an azo componentcyanacetylthiourea having the structural formula WILLIAM H. VON GLAI-IN.LESTER N. STANLEY.

REFERENCES CITED Thefollowing references are of record in the file ofthis patent:

UNITED STATES PATENTS Number Name Date 1,989,065 Schmidt et a1 Jan. 22,1935 2;1 08,602 Mannes et a1 Feb. 15, 1938 2,217,189 Sus Oct. 8, 19402312,040 Kendall et a1 Feb. 23, 1943 2,436,007 Kendall et al. Feb. 17,1948: 2,453,661 Glass Nov. 9, 1948

1. A DIAZOTYPE PHOTPRINTING MATERIAL COMPRIS-
 1. A PROCESS FORRECOVERING THE COMPONENTS OF OF THE BENZENE SERIES AND AN AZO COMPONENTSEA COMPLEX OF HYDROGEN FLUORIDE WITH POLYOLEFINIC LECTED FROM THE CLASSCONSISTING OF CYANACETYLCYCLIC HYDROCARBONS CONTAINING CONJUGATED ANDAMIDES OF THE FOLLOWING FORMULA NON-CONJUGATED UNSATURATION, WHICHCOMPRISES IN-